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Herein, we establish a molten\u2010salt\u2010assisted strategy to construct a multifunctional cathode host (PNCNs@CeO\n                    <jats:sub>2\u2010x<\/jats:sub>\n                    ), where oxygen\u2010deficient CeO\n                    <jats:sub>2\u2010x<\/jats:sub>\n                    nanoparticles are confined within a hierarchically porous carbon framework and encapsulated by graphene\u2010like carbon nanosheets. This deliberately orchestrated architecture unifies spatial confinement and oxygen\u2010vacancy\u2010enabled catalysis to form conductive microreaction domains featuring continuous ion\/electron transport pathways and abundant active interfaces. Through in situ characterizations and machine\u2010learning\u2010assisted molecular dynamics simulations, we demonstrate that oxygen vacancies in CeO\n                    <jats:sub>2\u2010x<\/jats:sub>\n                    induce favorable charge redistribution, strengthen Na\n                    <jats:sub>2<\/jats:sub>\n                    S\n                    <jats:sub>x<\/jats:sub>\n                    adsorption, lower the energy barrier for Na\n                    <jats:sub>2<\/jats:sub>\n                    S\n                    <jats:sub>2<\/jats:sub>\n                    \/Na\n                    <jats:sub>2<\/jats:sub>\n                    S conversion, and promote a highly reversible solid\u2013liquid\u2013solid conversion process, thereby effectively suppressing polysulfide dissolution. Consequently, the PNCNs@CeO\n                    <jats:sub>2\u2010x<\/jats:sub>\n                    \u2010S cathode exhibits an impressive reversible capacity of 1167 mAh g\n                    <jats:sup>\u22121<\/jats:sup>\n                    at 0.1\u00a0A g\n                    <jats:sup>\u22121<\/jats:sup>\n                    and outstanding cycling stability, maintaining 86.2% capacity retention after 9000 cycles at 5\u00a0A g\n                    <jats:sup>\u22121<\/jats:sup>\n                    . This work establishes a confinement\u2010catalysis design paradigm for regulating sulfur electrochemistry for long\u2010life RT Na\u2010S batteries.\n                  <\/jats:p>","DOI":"10.1002\/adma.75129","type":"journal-article","created":{"date-parts":[[2026,9,25]],"date-time":"2026-09-25T06:10:01Z","timestamp":1790316601000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Hierarchical Confinement and Oxygen\u2010Vacancy Catalysis for Highly Reversible Room\u2010Temperature Sodium\u2010Sulfur Batteries"],"prefix":"10.1002","author":[{"given":"Wei","family":"He","sequence":"first","affiliation":[{"name":"State Key Laboratory of Structural Chemistry, and Fujian Provincial Key Laboratory of Materials and Techniques toward Hydrogen Energy Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences  Fuzhou Fujian China"},{"name":"College of Environmental and Chemical Engineering Nanchang Hangkong University  Nanchang China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Huiling","family":"Fang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Structural Chemistry, and Fujian Provincial Key Laboratory of Materials and Techniques toward Hydrogen Energy Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences  Fuzhou Fujian China"},{"name":"College of Chemistry and Materials Science Fujian Normal University  Fuzhou China"},{"name":"Fujian College University of Chinese Academy of Sciences  Fuzhou Fujian China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zijing","family":"Huo","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Structural Chemistry, and Fujian Provincial Key Laboratory of Materials and Techniques toward Hydrogen Energy Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences  Fuzhou Fujian 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and Techniques toward Hydrogen Energy Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences  Fuzhou Fujian China"},{"name":"Fujian College University of Chinese Academy of Sciences  Fuzhou Fujian China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0005-0533-969X","authenticated-orcid":false,"given":"Ahmed","family":"Abdel\u2010Aziz","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Structural Chemistry, and Fujian Provincial Key Laboratory of Materials and Techniques toward Hydrogen Energy Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences  Fuzhou Fujian China"},{"name":"Fujian College University of Chinese Academy of Sciences  Fuzhou Fujian 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